The present invention relates to a novel imidazole/monocarboxylic acid derivative, and also to a surface treatment agent that has this imidazole/monocarboxylic acid derivative as an active ingredient and is for improving the adhesion between a metal such as copper, steel or aluminum or an inorganic material such as glass fiber, silica, aluminum oxide or aluminum hydroxide and a resin, a resin additive that has this imidazole/monocarboxylic acid derivative as an active ingredient and is for improving the adhesive strength and mechanical strength of a resin such as an epoxy resin, and a resin compositionxe2x80x94in particular a polyimide resin compositionxe2x80x94that contains this imidazole/monocarboxylic acid derivative.
A board of an electronic device is made by heating copper foil and a phenol-resin-impregnated paper substrate, an epoxy-resin-impregnated glass substrate or the like while pressurizing to produce a copper-clad laminate, and then forming an electric network by etching, and mounting elements such as semiconductor devices on top.
During the manufacturing process, the copper foil is bonded to the substrate, and they are heated, immersed in acidic or alkaline solutions, a resist ink applied thereto, soldered, and hence the copper foil and the substrate are required to have various properties. To satisfy these requirements, with regard to the copper foil, studies have been carried out subjecting the copper foil to brass layer formation treatment (Japanese Patent Publication Nos. S51-35711 and S54-6701), chromate treatment, zinc-chromium mixture coating treatment in which the coating includes zinc or zinc oxide and chromium oxide (Japanese Patent Publication No. S58-7077), treatment with a silane coupling agent, and the like. Moreover, with regard to the resin, the requirements are satisfied by changing the type of resin and/or curing agent and/or the mixing proportions thereof, by adding additives, and so on. Moreover, in the case of glass fiber, surface treatments using a silane coupling agent or the like have been studied. However, in recent years, there have been advances in miniaturization of printed circuits, and the properties required of the boards used in electronic devices have become ever more stringent.
To cope with the required improvement in etching precision that goes along with the above, the Matte side of the copper foil bonded to the prepreg is required to have a lower surface roughness (i.e. a low profile). However, the surface roughness of the Matte side produces an anchoring effect so as to bond the prepreg tightly, and hence the requirement of a low profile goes against improving the adhesive strength, meaning that the reduction in the anchor effect upon lowering the profile must be compensated for by improving the adhesive strength by another means.
Moreover, a composite material in which an inorganic material such as silica or alumina is filled into an epoxy resin matrix is used as an electrically insulating casting material used, for example, in high voltage/high capacity devices and in sealing semiconductors in power plants. Various electrical and mechanical properties are required of such a material, and to satisfy these requirements it is necessary to improve the adhesion between the inorganic material and the resin. Measures such as adding a silane coupling agent into the resin or subjecting the inorganic material to surface treatment with a silane coupling agent have been proposed, but further improvement of the resin/inorganic material interface is required.
An object of the present invention is to provide a novel imidazole/organic monocarboxylic acid salt derivative reaction product that is capable of meeting these requirements, that is, that improves the adhesion between a metal such as copper, steel or aluminum or an inorganic material such as glass fiber, silica, aluminum oxide or aluminum hydroxide and a resin. Further, another object of the present invention is to provide a method for producing this imidazole/organic monocarboxylic acid salt derivative reaction product, and a surface treatment agent, resin additive and resin composition that use this imidazole/organic monocarboxylic acid salt derivative reaction product.
The inventors of the present invention carried out assiduous studies, and as a result discovered: if a metal or an inorganic material is subjected to surface treatment with an imidazole/organic monocarboxylic acid salt derivative reaction product obtained by reacting a specific imidazole compound with a silane compound having a glycidoxy group and then reacting with an organic monocarboxylic acid, then the adhesion of the metal or the inorganic material to a resin is improved; and furthermore, if such an imidazole/organic monocarboxylic acid salt derivative reaction product is added to a resin such as an epoxy resin, then the curing reaction of the resin is promoted and moreover the adhesive strength and the mechanical strength of the resin are improved.
The present invention was achieved based on the above findings, and is summarized as follows:
(1) An imidazole/organic monocarboxylic acid salt derivative reaction product obtained by reacting an imidazole compound represented by undermentioned general formula (1) with a silane compound having a glycidoxy group represented by undermentioned general formula (2) at 80 to 200xc2x0 C., and then reacting with an organic monocarboxylic acid at 50 to 200xc2x0 C.; 
where, in general formulae (1) and (2), R1, R2 and R3 are each independently a hydrogen atom, a vinyl group, or an alkyl group having 1 to 20 carbon atoms, while R2 and R3 may together form an aromatic ring; R4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms; m is an integer between 1 and 10; and n is an integer between 1 and 3.
(2) A method for producing the imidazole/organic monocarboxylic acid salt derivative reaction product as described in (1) above, comprising: reacting an imidazole compound represented by undermentioned general formula (1) with a silane compound having a glycidoxy group represented by undermentioned general formula (2) at 80 to 200xc2x0 C.; and subsequently reacting with an organic monocarboxylic acid at 50 to 200xc2x0 C.; 
where, in general formulae (1) and (2), R1, R2, R3, R4, R5, m and n are as defined in (1) above.
(3) A surface treatment agent having the imidazole/organic monocarboxylic acid salt derivative reaction product as described in (1) above as an active ingredient.
(4) A resin additive having the imidazole/organic monocarboxylic acid salt derivative reaction product as described in (1) above as an active ingredient.
(5) A resin composition containing the imidazole/organic monocarboxylic acid salt derivative reaction product as described in (1) above.
(6) A polyimide resin composition containing the imidazole/organic monocarboxylic acid salt derivative reaction product as described in (1) above.
Following is a more detailed description of the present invention.
In above-mentioned general formulae (1) and (2), if any of R1, R2 or R3 is an alkyl group, then this alkyl group has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Moreover, if R2 and R3 together form an aromatic ring, then this aromatic ring is preferably a benzene ring.
The imidazole/organic monocarboxylic acid salt derivative reaction product of the present invention can be manufactured by reacting an imidazole compound represented by undermentioned general formula (1) with a silane compound having a glycidoxy group represented by undermentioned general formula (2) at 80 to 200xc2x0 C., and then reacting with an organic monocarboxylic acid at 50 to 200xc2x0 C. The reaction mechanism is complicated, with networking through siloxane bonds occurring in part, but the main reactions can be represented by the following formulae. 
In the above general formula, A indicates the organic monocarboxylic acid.
Preferable examples of the imidazole compound represented by above-mentioned general formula (1) include imidazole, 2-alkylimidazoles, 2,4-dialkylimidazoles and 4-vinylimidazole. Of these, particularly preferable ones include imidazole; as 2-alkylimidazoles, 2-methylimidazole, 2-ethylimidazole and 2-undecylimidazole; and as a 2,4-dialkylimidazole, 2-ethyl-4-methylimidazole. Moreover, examples of the silane compound having a glycidoxy group represented by above-mentioned general formula (2) are 3-glycidoxypropyltrialkoxysilanes, 3-glycidoxypropyldialkoxyalkylsilanes and 3-glycidoxypropylalkoxydialkylsilanes. Of these, particularly preferable ones include, as 3-glycidoxypropyltrialkoxysilanes, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; as a 3-glycidoxypropyldialkoxyalkylsilane, 3-glycidoxypropyldimethoxymethylsilane; and as a 3-glycidoxypropylalkoxydialkylsilane, 3-glycidoxypropylethoxydimethylsilane. Moreover, as the organic monocarboxylic acid, a saturated aliphatic monocarboxylic acid, an unsaturated aliphatic monocarboxylic acid, an aromatic monocarboxylic acid or the like can be used. Of these, particularly preferable ones include acrylic acid, methacrylic acid, isobutyric acid, octylic acid, formic acid, glyoxylic acid, crotonic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, cyclohexanecarboxylic acid, toluic acid, phenylacetic acid and p-t-butylbenzoic acid.
The reaction of the imidazole compound and the silane compound having a glycidoxy group is carried out using the synthesis method disclosed in Japanese Patent Application Laid-open No. H5-186479. Specifically, the imidazole compound and the silane compound having a glycidoxy group can be reacted by heating the imidazole compound to a temperature of 80 to 200xc2x0 C. and then instilling the silane compound having a glycidoxy group into the imidazole compound in a ratio of 0.1 to 10 mol of the silane compound per 1 mol of the imidazole compound, and in this case the reaction time is adequate at about 5 minutes to 2 hours. There is no particular need for a solvent, but an organic solvent such as chloroform, dioxane, methanol or ethanol may be used as a reaction solvent. Note that the reaction is damaged by water, and is thus preferably proceeded under an atmosphere of a gas containing no moisture such as dried nitrogen or argon so that no moisture gets into the system. The desired imidazole-silane compound represented as the above general formula is obtained as a mixture with other compounds having siloxane bonds, but the desired compound can be isolated and purified by a known method that utilizes the difference in solubility between the compounds or column chromatography. Note, however, that in the case of use as a surface treatment agent or a resin additive, there is no real need to isolate the imidazole-silane compounds from one another, and the reaction mixture containing complex compounds partially networked through Sixe2x80x94O bonds can be used as it is in the next reaction step, namely the reaction with the organic monocarboxylic acid. The imidazole-silane compounds so obtained reacts with the organic monocarboxylic acid by heating the imidazole-silane compounds to a temperature of 50 to 200xc2x0 C., and then adding, for example, an equivalent molar amount of the organic monocarboxylic acid; the reaction time is again adequate at about 5 minutes to 2 hours. Again, there is no particular need for a solvent, but an organic solvent such as chloroform, dioxane, methanol and ethanol may be used as a reaction solvent. Moreover, again the reaction is damaged by water, and is thus preferably advanced under an atmosphere of a gas containing no moisture such as dried nitrogen or argon so that no moisture gets into the system.
The imidazole/organic monocarboxylic acid salt derivative reaction product of the present invention usefully serves as a surface treatment agent or a resin additive for improving adhesion. When used as a surface treatment agent, the imidazole/organic monocarboxylic acid salt derivative reaction product of the present invention is preferably used as a solution with a suitable solvent. Moreover, when used as a resin additive, the reaction product may either be used as is or as a solution in a suitable solvent, with the amount added being 0.01 to 50 parts per weight, preferably 0.1 to 20 parts per weight, per 100 parts per weight of the resin. Moreover, substrates to which the surface treatment agent of the present invention can be applied include substrates made of a metallic material such as copper, iron or aluminum or an inorganic material such as glass fiber, silica, aluminum oxide or aluminum hydroxide. Moreover, when adding the imidazole/organic monocarboxylic acid salt derivative reaction product of the present invention to a resin to improve the adhesion and strength of the resin, resins that can be used include polyimide resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyphthalate resins, polyurethane resins, silicon resins, vinyl chloride resins, vinylidene chloride resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polystyrene resins, AS resins, ABS resins, AXS resins, methacrylate resins, polyethylene resins, EVA resins, EVOH resins, polypropylene resins, fluororesins, polyamide resins, polyacetal resins, polycarbonate resins, saturated polyester resins, polyphenylene ether resins, polyphenylene sulfide resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, liquid crystal plastic resins, cellulose plastic resins, thermoplastic elastomer resins, alkyd resins, furan resins, acrylic acid ester resins, petroleum resins, dicyclopentadiene resins, diethylene glycol bis(allyl carbonate) resins, and polyparabanic acid resins.